Document Dvag3rk3VyVK0KJ0Og4B2mJVO

eta JSoftho s(^ncc). Ivord: irtge. fngfonrf UJOCKMS yfvantfl, USA utc of Swiuertand 'RYSSflBfRGHB USA JNSt unq papers on ach your. imicaAct thus -ut tho rapidly ilmlca Acta: -ossos eloctrodos ontvoloncy steles oclrodes in itlon copy It/69 w Watir Rtttorch Ptrgamoii Tress 1970. Vol. 4, pp. 265-269. Printed in Great Britain A REVIEW OF CHLORINATED BII'IIENYL CONTAMINATION IN NATURAL WATERS Gilman D. Vutii and G. Faro Lie Water Chemistry Laboratory University of Wisconsin, Madison, Wis. 53706, U.S.A. (Rtcth'td 10 Norrmbtr 1969) Abstract--A review of the present state of knowledge concerning environmental contaminalion by organochlorine compounds indicates (hat the chlorinated biphenyls may be one of the more widespread contaminants. The significance of this contamination has not yet been evaluated due, in part, to the lack of systematic analytical procedures for the quantitative and qualitative determinations of the components of chlorinated biphenyl mixtures. The possibility of (he chlorinated biphenyls producing serious errors in chloiinated pesticide analyses is emphasized. INTRODUCTION Cmi mical determinations of the types and concentrations of chlorinated pesticides in natural waters have become increasingly important to fish management, wildlife ecology, and water pollution control. Based on gas chromatographic (GLC) analyses of environmental samples, pp'DDE is generally considered to be one of the more widespread contaminants. Jlowi ver, implicit in every GLC analysis is the possibility that unresolved and/or unidentified components which have specific retention volumes similar to that of the desired substance may introduce serious errors in the interprets* tion of the chromatogram. Increasing numbers of investigators have reported the presence of organochlorine compounds in environmental samples which cannot be identified as the common chlorinated pesticides. Although the unidentified compounds have been attributed from presumptive evidence to the metabolites of common pesticides, plasticizers, or chlorinated biphenyls, proper chemical identifications have not been reported. Therefore, when studying natural water systems which receive industrial wastes, it may be more correct to consider unidentified compounds as chlorinated organic contaminants until confirmation techniques are developed. Within the last three years, the chlorinated biphenyls (or polychlorinated biphenylsPCI!) have received considerable study. The preliminary evidence indicates that this group of organochlorine compounds may be widespread in the environment. For example, Widmamc (1967) reported that mass-spectrum analyses of compounds eluting front GLC of fish and bird extracts indicated that unknown organochlorine compounds were present which behaved as chlorinated biphenyls of higher chlorine content. More recently, mass numbers and chlorine numbers per molecule for each peak in the chromatograph of commerical chlorinated biphenyl were reported (Jensen cl a/., 1968). However, to our knowledge, no spectral data or other confirm* lory data for positive structural identification of these compounds have ever been published. With this improper basis of identification, a number of other publications have followed which identify unknown compounds as chlorinated biphenyls. Since mixtures of chlorinated biphenyls may contain greater than 20 compounds which can only be watvr 4/4-a 265 \ MGNS QB71ZZ (tv'i^wr,t>y ':`r v*?*** 266 Gilman P. Vcmi end O. Fred Lee resolved by GI.C with great difficulty, assignment of unidentified peaks to ono of the chlorinated biphenyls has been accomplished by comparison of a chlorinated biphenyl with the nearest relative retention time. For example, llOltHN and MARsnr.N (1967), who had earlier reported the presence of unknown compounds in fish (Holton, 1966), reported the presence of chlorinated biphenyls in seals with.no supporting data other than relative retention data from GLC columns. Robinson ft at. (1967) reported compounds of unknown identity in marine organisms which gave GLC retention times longer than pp'DDE and microcoulometric response. The authors indicated that the chromatographic characteristics of the unknowns suggested they were not metabolites of the "cyclodicne-type" pesticides as has been proposed by Roburn (1965). Holmis et at. (1967) attributed unknown peaks from GLC to the chlorinated biphenyls and noted that the substances seemed to accumulate in organisms associated with natural waters (seals, fish and birds) to a greater extent than in domestic animals. This work reported relative rcntenlion data with no supporting data. Rrmirougii et at. (1968 a) and Riserrougm et at. (1968 b) reported organochlorinc compounds in fish, birds and bird eggs which were attributed to the chlorinated biphenyls. With no supporting data and despite the absence ofstructural confirmations for the chlorinated biphenyls, the investigators reported concentrations of the unknowns (as chlorinated biphenyls) as well as ratios of DDT to chlorinated biphenyls. From these ratios, it was concluded that a chlorinated biphenyl fallout pattern existed around industrial centers and that air transport of the contaminants was significant. Kofman et at. (1969) presented GLC chromatograms of extracts from environ mental samples as well as mass numbers and numbers of chlorine atoms per molecule for each peak of the chromatogram. Although no spectral data were presented, the mass number data strongly suggested that chlorinated biphenyls were present. This paper also presented the results of the analyses for each unknown as being "present" or "absent" in a particular sample, rather than attempting to quantitate the amount of material present. THF. CHLORINATED BIPHENYLS Since contamination of the environment by chlorinated biphenyls has been implicatcd in the brief review presented, the need for the environmental scientist to become familiar with the present state of knowledge concerning these molecules is apparent. Mixtures of chlorinated biphenyls have been manufactured since 1929 and present registered trademarks for commercial brands include: Arochlor (Monsanto), Chlorcxtol (Allis-Chalmcrs), Dykanol (Corncll-Dubilicr Division, Federal Pacific Electric), Incrtccn (Westinghouse), Noflamo! (Wagner Electric), Pyramol (G. E.), Therminol (Monsanto) in the U.S.; and Clophen (I. G. Farbenidustrie A. G., Ger many), Fcnclor (CafTaro, Italy), Kanncchlor (Kancgnfuchi Chemical Co., Japan), Pyrolene (Prodclcc, France), and Soval (Russia) (Hubbard, 1964). T he chlorinated biphenyls have been used as plasticizers for adhesives, polyvinyl acetates, acrylic resins, in scaling compounds, pipe joint compounds, printing ink, rubber manufactur ing, high pressure-high temperature lubricants, fungicidal insulations, anti-corrosion, nail coatings, water proofings, diffusion pump fluid, stabilization of polymers, dielectrics, I preventing | (Monsanicet at., 1955; The toxis has not be indicate th; "safe" is I. highly chic with chlori reported re biphenyls effects of ^ cited) to t 5460 to be More re biphenyls t tion, and t factor of 1 dieldrin an Howeve with orgar possibility biological review of other meti enzyme in great as pt facts make cules have concentrat Some e studies of biphenyl, analyses, have been make the ofehemie* For exa step whicl residues ( was treate It was cot nitration! MONS 0871^3 me or (he biphenyl N(l%7), N, 1966), ala other t marine re >ulo* fillies of cMicklcs ormalcd soriiilcd inimals. .hlorinc Hina led niations of Hie -rinulcd fallout ntnants nviron* olcculc ed, Ihe I. This fwnt" mount I A Review of Chlorinated Diphenyl Contamination in Natural Waters dielectrics, heat transfer media. coax*cablc insulations, paints and varnishes, iecpreventing coatings, and is an evaporation retardant for pesticide applications (Monsanto O/l'L-306; IhnmAno, 1964; Hopkins arid Hoffman, 1955; Sullivan r/ ah, 1955). The toxicity and sublcthal effects of the chlorinated biphenyls to biological systems has not been thoroughly evaluated (Rncnri., 1969). Inhalation tests on animals indicate that maximum concentrations of chlorinated biphenyls as vapor which are "safe" is 10 mg/m1 for the lower chlorinated biphenyls and 0.5 mg/m9 for the more highly chlorinated biphenyls (IIumiard, 1964). Continuous or repeated skin contact with chlorinated biphenyl leads to a condition called "chioracne" which has been reported repeatedly with industrial workers handling products containing chlorinated biphenyls (Mugs ct ah, 1953). Sullivan and Hornstlin (1953) found no toxic effects of Arochlor 5460 on flics, but the chlorinated terphenyl9 were toxic (no levels cited) to the elm leaf beetle (L>uim, 1957). Dloniitr ct ah (1946) found Arochlor 5460 to be non-toxic at 0.1 ppm (24 hr) to the larvae of Anopheles qundrimacHiatus. More recently, Licktiinsiiin et al. (1969) reported Ihe toxicity of the chlorinated biphenyls to houseflies (/). melanogaster) decreased with increasing degree of chlorina tion, and that the chlorinated biphenyls appear to be less toxic than dicldrin by a factor of 1000. The chlorinated biphenyls were found to increase the toxic effect of dicldrin and DDT on houseflies. However, in addition to investigating the sources of environmental contamination with orgnnochlorine compounds, the environmental scientist is concerned with the possibility that these organochlorine molecules may exhibit detrimental effects on biological communities at sublcthal levels. Kupitr (1967) has presented on extensive review of the effects of chlorinated pesticides on steroid hydroxylase induction and other metabolic systems. Also, Risliirougii ct ah (1968 b) have demonstrated that enzyme induction by the chlorinated biphenyls (Arochlor 1262) was five times as great as pp'DDE or technical DDT as determined via oestradiol degradation. These facts make tolerance limits set by bioassay less significant since organochlorine mole cules have the capacity to produce physiological effects in organisms at sublethal concentrations. impliccoine went. relent into), 'acific *:'>. Gcr* pan), intrd rylic Mur* ion, iers, ANALYTICAL PROCEDURES Some controversy has been generated over the analytical procedures utilized in studies of organochlorine contaminants which have been attributed to the chlorinated biphenyl. In general, the procedures arc similar to typical chlorinated pesticide analyses. However, chemical reactions such ns dehydrohaJogenation and nitration have been introduced prior to electron capture gas chromatography in attempts to make the procedures more selective for the chlorinated biphenyls. It is the addition of chemical treatment steps which has caused disagreement in the literature. For example, after extract clean up, Jfnsen and Widmark (1967) used a nitration I step which is similar to that used in removing DDT and metabolites from toxaphcnc I residues (Erro et ah, 1967; Kawano et ah, 1969). Briefly, the concentrated extract { was treated with a mixture of H]S04 and IINO* (cone. 1:1, v/v) at 0*C for 5 min. | It was concluded incorrectly that only PCB and BHC isomers are unaffected by the nitration step. Riscdrough et at. (1969) have reported the use of similar procedures. V MOMS 087124 261 Gilman D. Venn and 0- Fain Lie To I he contrary, Reynolds (1969) has been unable to repeat the nitration step reproducibly for a number of reasons. First, the reaction is not specific for the PCD and 111 1C isomers, since hcptachlor epoxide remains unaffected by nitration. Also, the work of Revenue (Faro, 1967; Kawano, 1969) has demonstrated that toxaphcnc, the reaction ptoduct of the chlorination of camphcnc which produces in excess of 20 unresolved peaks on GLC, is apparently unaltered by nitration. Second, Reynolds found some loss of the earlier eluting chlorinated biphenyls during nitration. Third, and most significant, peaks with longer retention volumes appeared in the chromato grams after nitration. These peaks resulted from the nitration of other aromatic mole cules in the mixture because nitro groups reduce the vapor pressures in the gas phase (GLC) and the aromatic nitro grouping lias a high affinity for the secondary electrons in the electron capture detector. Results of studies of this laboratory {Vtrni and Lin, 1969) have substantiated earlier reports (Dlguksii, 1969) thnt fish and natural waters in several ureas of Wisconsin contain unidentified orgnnochlorinc contaminants. Using essentially the same pro cedures discussed by Reynolds (1969), the resulting chromatograms contain many peaks which have retention volumes similar to those of components of several com mercial chlorinated biphenyl mixtures. However, components with corresponding retention volumes were also observed in chromatograms of technical chlordanc, hcptnchlor epoxide, benzene hexachloride, and toxaphenc, as well as analytical standards of a number of the DDT family of pesticides. Accordingly, qualitative and quantitative interpretations of such chromatograms from Wisconsin fish and water await more detailed and systematic investigations of the extracts. CONCLUSIONS The preliminary evidence of the past several years, which has been reviewed in this communication, indicates that the environment associated with natural waters is becoming contaminated with unidentified organochlorinc compounds from unknown sources. The facts that chlorinated biphenyls have been strongly implicated as con taminants, that the chlorinated biphenyls have been widely used in industry and have been prepared commercially since 1929, and that the mixtures produce GLC peaks with retention volumes similar to common chlorinated pesticides create a need for basic studies concerning analytical procedures for chlorinated hydrocarbons. Also, it is apparent that comprehensive and systematic investigations into the chemistry and the physiological effects of the contaminants as well as the degree and sources of the contamination are essential before control measures can be considered. REFERENCES Dunmse P. (1909) Personal communication from the Wisconsin Department of Natural Resources, Madison. v Dionm.r C. C., Jonix H. A. and Inciio H. H. (1946) Organic compounds effective against larvae of Anopheles quadtImarulatus. J, eeon. Ent. 39, 459-462. Duoa J. 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(1968 a) Pesticides: Trans* Atlantic movement* in the Ne>rlhcast Trades. Science 159, 1253-1214. Risi naoiKiH R. W., R it cut! P.t Hi.aman $. G., Drakall D. B. and Kikvin M. N. (1968 b) Poly* chlorinated biphenyls in the p.lobnl ecosystem. Nature, Land. 220, 1098-1)02. Rimrrouom R. W., Rnciti P. and OLrorr H. S. (1969) Current progress in the determination of the polychlorinated biphenyls. Dull. Env. Contain. Toxical. 4, 192-201. Komnson J., R makdson A., CttABTHtc A. N., Coulson 3. C. and Pom G. R. (1967) Organo* chlorine residues in mnrine organisms. Nature, Ijmd. 214, 1307-1311. Robuan J. (1965) A simple concentration cell technique for determining small amounts of halide ions and its use in ilte determination of residues of organochlorinc pesticides in extracts of animal and plant tissue. Analyst 90,467-475. Sullivan W. N. and Hornstmn 1. (J9S3) A comparison of evaporation rates and toxicity to house flies of lindane and lindane-chlorinated polyphenyl deposits. J. econ. Eat. 46, 882-894. Sullivan W. N., Hornsuin I. and Yeomans A. H. (1955) Improved deposits for controlling insects outdoors. J. econ. Ent. 48, 153-155. Vettm G. D. and Lre. G. F. (1969) Chlorinated Organic Contaminants In the Milwaukee River, Progress Report to (he Wisconsin Deportment of Natural Resources, Madison, October, mimeo. Wiomark O. (J967) Pesticide Residues. J. Ass. Official Analyt. Chem. 50,1069. . t \ \ V' . ' r 1 ..... . y MONS 087126